Reactive disazo dyestuffs containing 1-aminoalkyl-6-hydroxypyrid-6-one and monochlorotriazinyl groupings

ABSTRACT

Disazo dyestuffs of the formula:   wherein N IS 0, 1 OR 2 P IS 0, 1 OR 2 Q IS 2 OR 3 AND Q is a member of the group consisting of 4,6-disulpho-1,3phenylene, 2,5-disulpho-1,4-phenylene,   D R A W I N G in which Q1 is a direct link or -CH CH-, -NH-CONH-, -S-, OCH2CH2O-, -CH2- or -CH2CH2- . These dyestuffs are greenish-yellow cellulose-reactive dyes of good fastness to washing, light, hypochlorite bleaching and to acid and alkali treatments. Mixtures with phthalocyanine dyes exhibit better resistance to catalytic wet fading than similar dyes based on pyrazolone coupling components.

United States Patent [191 Crabtree [451 Sept. 16, 1975 1 REACTIVE DISAZO DYESTUFF S CONTAINING l-AMINOALKYL-6-HYDROXYPYRID-6-ONE AND MONOCHLOROTRIAZINYL GROUPINGS [75] lnventor: Allen Crabtree, Manchester,

England [73] Assignee: Imperial Chemical Industries Limited, London, England [22] Filed: June 4, 1973 [21] Appl. No.: 366,686

Related US. Application Data [63] Continuation-impart of Scr. No. 160,560, July 7, 1971, abandoned, which is a continuation-in-part of Ser. No. 860,030, Septv 22, 1968, abandoned.

[30] Foreign Application Priority Data Dec. 9, 1968 United Kingdom 58281/68 [52] US. Cl 260/153; 260/296 R; 260/507 R; 260/508 [51] Int. Cl. C09B 62/08; DO6P 1/38; DO6P 3/60 [58] Field of Search 260/153, 156, 146 T [56] References Cited UNlTED STATES PATENTS 2,431,190 11/1947 Morgan 260/156 X 3,149,100 9/1964 Hindermann et a1. 260/153 3,226,176 12/1965 Hindermann et a1. 260/153 X 3,362,948 1/1968 Andrew et a1 260/146 T 3,487,066 12/1969 Ritter et 260/156 3,639,662 2/1972 Griffiths 260/146 T 3,664,995 5/1972 Andrew et a1.. 260/146 T 3,725,383 4/1973 Austin et a1 1. 260/146 T 3,729,476 4/1973 Austin et a1. 260/156 X Primary Examiner-Floyd D. Higel Arlurney, Agent, or Firm-Cushman, Darby & Cushman [5 7] ABSTRACT Disazo dyestuffs of the formula:

SOHH

wherein n is O, 1 or 2 p is O, 1 or 2 qis 2or3 and Q is a member of the group consisting of 4,6-disu1pho-1,3-pheny1ene, 2,5-disulpho-1,4-phenylen'e,

in which Q is a direct link or CH=CH-, N- H-CONH-, s OCH2CH2O, -CH2 or -CH2CH2.

These dyestuffs are greenish-yellow cellulose-reactive dyes of good fastness to washing, light, hypochlorite bleaching and to acid and alkali treatments. Mixtures with phthalocyanine dyes exhibit better resistance to catalytic wet fading than similar dyes based on pyrazolone coupling components.

6 Claims, No Drawings I hydroxypyridone series, and is more particularly con cerned with the provision of a range of disazo cellulose reactive dyes which are primarily intended to bedyed from hot, alkaline saline dyebaths to provide very bright greenish-yellow shades on cotton, viscose rayon and other cellulose materials such as linen. These new dyestuffs are strong tinctorially, and provide shades'on these materials which have an adequate light fastness, very good fastness to washing and to bleach treatments, to acid and alkali treatments.

STATE OF THE ART This invention is a development arising from the gen eral class of reactive dyestuffs described in U.K. Patent Specification No. 854,432 which consist, broadly of two similar monoazo dye radicals linked through two monochloro-s-triazine residues themselves connected by a diamine residue. This broad class has proved a useful source of dyes which dye cellulose from hot alkaline saline dyebaths, although to obtain commercially use.- ful dyes it is necessary to carefully balance the effect of the monoazo dye residue with theeffect of the diamine residue.

Some improved dyes of this type are described, for example in US. Pat. Nos. 3,639,662 and 3,658,782 in which the essentially novel concept lies in the use of certain diamines used as the linking group. In these specifications greenishyellow shades are obtained by linking together monoazo dyes of the phenylazopyrazolone series by chloro-s-triazine groups and the appro priate diamine.

However these dyes have certain deficiencies,.notably in fastness to bleach treatments (including c.g. the

AATCC 4 washing test) and to alkali treatments. Furthermore, mixtures with phthalocyanine dyes, commonly used to obtain bright green shades, have unsatisfactory light fastness in moist weakly alkaline conditions. This effect is known in the art as catalytic wetfading. i

As compared with known pyrazolone dyes of the above-mentioned specifications, the new dyestuffs are stronger tinctorially have better fastness to bleach treatments. and to alkali treatments and exhibit a lower degree of catalytic wet fading in mixtures with phthalocyanine dyes.

The concept of use of hydroxypyridones to manufacture azo dyes is not new; for example, US. Pat. No. 2,431,190 discloses the use of certain 4-hydroxypyridones as couplers in the manufacture of diazotype prints. However this kind of coupling component is quite useless for the manufacture of cellulose-reactive dyes since it has been found that. the 4-hydroxypyridone ring is unstable to alkali and decomposes under the conditions typical for dyeing or printing with cellulose-reactive dyes. More :recently US. Pat. No. 3,487,066 discloses that disperse dyes obtained from 2,6-dihydroxy3-cyano-4-methylpyridine and certain benzenoid diazo components free from SO H or CO H groups provide reddish-yellow or greenish-yellow dyeings on polyester fibres. The new dyes differ in the use of a sulphonated naphthylamine as diazo component,

the use of pyridone coupling components which are differently substituted in the .l and 3. positions; the fact that the dyes of US. Pat. No. 3,487,066 are waterinsoluble and cannot dye cellulose and the new dyes are water-soluble and cannot dye polyester; their general structure is quite different to any disazo dyestuff described in US. Pat; No. 3,487,066; finally reactive dyes based on the coupling component of US. Pat. No. 3,487,066 and disulphonated naphthylamines are similar to pyrazolone dyes in their poor fastness to bleach and alkali treatments.

THE INVENTION According to the present invention there are provided disazo dyestuffs of the formula:

( zlp wherein n is 0, l or 2 p is 0, 1 or 2 q is 2 or 3 and Q is a member of the group consisting of 4,6-disulphol ,S-phenylene, 2,5-disulpho-l ,4-phenylene,

n which Q is a direct link or -CH=CH-, N- l-CONH, S, OCH CH O, CH or CH CH The preferred dyes, in general, are those in which n is this SO H group being in the 5 or 6 position of the iaphthalene ring, p is l or 2 and q is 2 or 3 so that C H ethylene.

The improvement in bleach fastness obtained by use If Tobias acid type diazo components is most surprisng since this effect is not found in comparable dyes ontaining a pyrazolone residue, or the 3-cyano-4- methyl-2,6-dihydroxypyridine nucleus.

The new dyestuffs can be obtained by the convenional coupling and condensation reactions starting rom 2 moles of a diazo component of the formula:

SO H

( IS LI nd a coupling component of the formula:

(CH-um 5) q zi z 2 moles of cyanuric chloride and 1 mole ofa diamine of ormula NH: NH:

In general, the coupling step can be effected before r after all the condensation steps have been carried ut or, if desired, may be carried out between the conensation steps.

Diazotization of the amine of formula (4) can be caried out in the normal way, c.g. by adding an alkali ietal nitrite to a solution of the amine in aqueous hyrochloric acid and allowing reaction to take place at a :mperature from 0C to about 20C.

The coupling step can be carried out in a weakly alaline, neutral or acid, even strongly acid, solution; it is 4 preferably carried out at a pH of from to 8, e.g. in the presence of acetic acid or a mixture of acetic acid and sodium acetate to maintain the pH in this range.

The condensation steps may be carried out in an aqueous medium, advantageously in the presence of a dispersing agent or a water-soluble organic liquid such nos as acetone, when cyanuric chloride is one of the reactants. Hydrochloric acid is formed during the course of the reaction and is preferably neutralized by maintaining the reaction mixture at a pH of 6-8 by adding an acid-binding agent, e.g. sodium hydroxide or sodium carbonate at a suitable rate. A higher pH may be used if this is necessary to dissolve the amino compound being reacted. Condensations involving cyanuric chloride are most expediently carried out at from 0 to about 20C and those involving dichloro-s-triazine compounds at from about 30C to about 50C. These temperature ranges are not critical but operation at lower temperatures will extend the reaction time and at higher temperatures will increase the possibility of unwanted side-reactions taking place.

As examples of diazo components of formula (4) which may be used, there may be mentioned:

Tobias Acid (2-naphthylamine-l-sulphonic acid) 2-naphthylamine-1,5-disulphonic acid Z-naphthylamine-l ,6-disulphonic acid 2-naphthylamine-l ,5,7-trisulph0nic acid As coupling components of formula (5) which may be used, there may be mentioned:

l-B-aminoethyl l-fl-aminopropyl l-y-aminopropyl l-B-aminoethyl l-B-aminopropyl Ly-aminopropyl l-B-aminoelhyl l- B-aminopropyl l-y-aminopropyl 4-methyl-6-hydroxypyrid-2-0ne -3 ,4-dimethyl-6-hydroxypyrid-2-one 3-ethyl-4-methyl6'hydroxypyrid-Z-one prising natural or regeneratedcellulose such ascotton', linen and viscose rayon. For coloring such materials, the new dyestuffs are preferably applied, either by a printing or a dyeing process to the cellulose textile material in conjunction with a treatment with an acid binding agent, e.g. caustic soda, sodium carbonate, silicate or bicarbonate, which may be applied to the mate rial before, during or after the application of the dyestuff. When so applied the new dyestuffs react with the cellulose and yield greenish-yellow shades having the properties stated earlier. The new dyestuffs are especially valuable for dyeing from hot, saline, alkaline dyebaths under which conditions a high level of fixation is achieved.

The invention is illustrated but not limited by the following examples in which parts are by weight.

EXAMPLE 1 3.03 Parts of Z-naphthylamine-1,5-disulphonic acid are dissolved in 150 parts of water by addition of caustic liquor (70lw). 0.69 part of sodium nitrite is added and the solution is stirred vigorously at 05whilst 8 parts of hydrochloric acid (36Tw) are added. The mixture is stirred at 05for 1 hour and the excess of nitrous acid destroyed by the addition of sulpharnic acid.

This solution is added to a solution of 1.68 parts of l-B-aminoethyl-4-methyl-6-hydroxypyrid-2-one in 100 parts of water at C and the mixture is stirred for 1 hour at 5l0. The yellow precipitate is collected by filtration and dissolved in 200 parts of water by addition of caustic liquor (70Tw), the final solution having pH 12-14. The solution is cooled to 05and added during minutes to a stirred suspension of 2.5 parts of cyanuric chloride in 15 parts of acetone, 50 parts of ice, 50 parts of water and one part of dispersing agent, the pH being maintained at 9-10 during the addition by means of occasional addition of 2N hydrochloric acid as necessary. The solution is stirred for a further 30 minutes at pH 89 and filtered, then the pH is adjusted to 7 by addition of aqueous hydrochloric acid and a so- 6 lution of 1.56 parts of disodium, 1,4-phenylenediamine-2,5-disulphonate in 30 parts of water is added.

The mixture is heated to C and stirred at 35-40C for 5 hours, keeping the pH at 67 by additions of aqueous sodium carbonate solution. The dyestuff obtained is precipitated by salting and is filtered off and dried. 1t dyes cotton and viscose rayon in bright greenish-yellow shades of good fastness to light, washing, bleach, acid and alkali.

EXAMPLE 2 A mixture of 42.4 parts of disodium 4,4-diaminostilb ene-2,2-disulphonic acid and 37 parts of cyanuric chloride in 1,000 parts of water are stirred for 2 hours at 05C, keeping the pH at 6-7 by adding sodium carbonate solution.

A solution of 36.4 parts of l-B-aminoethyl- 3,4dimethyl-6-hydroxypyrid-2-one in 500 parts of water is added and the mixture is heated to 35C and stirred at 3540C for 4 hours, keeping the pH at 6-7 by adding sodium carbonate solution.

The mixture is cooled to 5C, then a solution of the diazonium salt from 44.6 parts of Z-naphthylamine-lsulphonic acid (obtained in similar manner to Example 1 is added and the mixture is stirred at 05C, pH 6-7 for 2 hours.

The dyestuff is isolated by salting, filtration and drying in the usual way. It dyes cotton and viscose rayon from hot alkaline saline dyebath's in bright greenish yellow shades of good fastness to washing, light, bleaching, acid and alkali.

The following table describes further examples of the invention which may be obtained in similar manner to Example 1 or 2 either by diazotizing the amine of column II and coupling with the pyridone of column 111 and reacting cyanuric chloride with 1 mole of the resulting azo compound and one-half mole of the diamine named in column IV, or by reacting cyanuric chloride with 1 mole of the pyridone and one-half mole of the diamine and coupling with thediazotized amine.

Example 3 2-naphthylaminc-l,5- CH- CH NH bcnzidine-4,4'disulphonic acid disulphonic acid 4 4,4-diaminodiphcnoxycthanc-Z,2-disulphonic acid 5 CH 4,4-diaminodiphenylurea 2,2'-disulphonic acid 6 4,4 '-diaminostilbene-2,2-disulphonic acid 7 CH CH(NH )CH;, 4,4'-diaminodiphcnylethane-2 2'disulphonic acid 8 Z-naphthylaminc-l- CH CH NH l,4phcnylenediamine-2,5-disulphonic acid sulphonic acid 9 benzidine 2,2disulphonic. acid H 4,4 diaminodiphenoxycthane-2,2'-disulphonic acid l 4,4'diaminodiphenylurea-2,2'-disulphonic acid 12 CH CH CH NH 4,4'-diaminodiphenylmethane-Z,2' disulphonic acid 13 2-naphlhylamincl ,6- CH 5,5 "diaminodiphenylurea-Z,2'-disulphonic acid disulphonic acid 14 CH CH( NH: )CH;, H 4,4'-diaminodiphcnylsulphide-2,2'-disulphonic acid 15 4,4-diaminodiphenylurea-2,2' disulphonic acid In Z-naphthylamincl f CH- ,CH. ,NH. H bcnzidinc-2,2'-disulphonic acid disulphonic acid 17 4,4'-diaminidiphcnuxycthancfl,2-disulphunic acid 18 Z-naphthylamincl ,5,7- CH l,3-phcnylcncdiamine-4,6-disulphonic acid trisulphonic acid l9 5,5'-diaminodiphenylurca-2 2'-disulphonic acid 30 hcnyjdinc-lZ'disulphonic acid 2| CH CH( NH )CH; H 22 CHgCH- NH: l,4-phenylcncdiaminc-2,5-disulphonic acid 23 CH CH C'H NH l l ,3-phcnylcncdiaminc-4,6-disulphonic acid I claim: 1. A disazo dyestuff of the formula:

CH2 HH Hots)" T o CQHMNH N I ll N N N T NH 1 1 TH c r N N i l fi H NH N/ c1 (HOMSM v 0 N=N (CH2),,H

S0,,H CH

' wherein n is O, l or 2 p is 0, 1 or 2 in which Q is a direct link or CH=CH-, N- H-CONH, S-, OCH CH 0, -CH or CH CH 2. A disazo dyestuff as claimed in claim 1 wherein n is 1, this SO H group being in the 5- or 6-posit ion of the naphthalene ring, p is 1 or 2 and q is 2.

3. A disazo dyestuff as claimed in claim 2, having the formula A Tr Dm Tr A wherein A is so H CH3 N O H S0,,H CH2CH2NH Tr is N I n c c and Dm is SOHH NH- NH so H 4. A disazo dyestuff as claimed in claim 2 having the formula A Tr Dm Tr A wherein A is SOHH

Tr is N l n C and Dm is so u NH- CH CH-- NH HO S 5. A clisazo dyestuff as claimed in claim 2 having the formula A Tr Dm Tr A wherein A is SO3H CH3 HO I so u Tr is and Dm is so H *NH GQNH sogH' 6. A disazo clyestuff as claimed in claim 2 having the formula A Tr Dm Tr A wherein A is UNTTED STATES PATENT OFFICE QER'HFICATE F CORRECTION Patent No. 3,905,950 Dated ptember 16, 1975 Inventor-(5) Allen Crabtree g 1 Of 2 Q It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading Under [63] Related U. S. Application Data, line 3, change "Sept. 22, 1968" to Q --Sept., 22, 1969--o Column l, line 7, change "Sept. 22, 1968" to "'-SePt 22 0 line 9, change "disazp" to --disazo--.

Column 8, between lines 45 and 55, the structural formula should read UNITED STATES PATENT OFFICE CETH ECATE 0F CORECTWN Patent 3,905,950 Dated September 16, 1975 Inventor(s) Allen crabtree Page 2 of 2 a It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9, between lines 10 and 20, the structural formula should read a Cl 3: 21 Ill l I C C e u Column 9, between lines 45 and 55, the structural formula should read a Cl /C N N a n e N c\ Column 10, between lines 30 and 40, the structural formula should read N C N igned and wit this twenty-seventh 0? April1976 0 [SEAL] Attest:

3 RUTH c. MASON c. MARSHALL DANN Atresnng Officer (ummissiuncr n 

1. A DIAZO DYESTUFF OF THE FORMULA:
 2. A disazo dyestuff as claimed in claim 1 wherein n is 1, this SO3H group being in the 5- or 6-position of the naphthalene ring, p is 1 or 2 and q is
 2. 3. A disazo dyestuff as claimed in claim 2, having the formula A - Tr- Dm - Tr - A wherein A is
 4. A disazo dyestuff as claimed in claim 2 having the formula A - Tr - Dm - Tr - A wherein A is
 5. A disazo dyestuff as claimed in claim 2 having the formula A - Tr - Dm - Tr - A wherein A is
 6. A disazo dyestuff as claimed in claim 2 having the formula A - Tr - Dm - Tr - A wherein A is 